CN109312164B - Resin composition for film, film with substrate, metal/resin laminate, cured resin, semiconductor device, and method for producing film - Google Patents
Resin composition for film, film with substrate, metal/resin laminate, cured resin, semiconductor device, and method for producing film Download PDFInfo
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- CN109312164B CN109312164B CN201780036206.1A CN201780036206A CN109312164B CN 109312164 B CN109312164 B CN 109312164B CN 201780036206 A CN201780036206 A CN 201780036206A CN 109312164 B CN109312164 B CN 109312164B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/24—Thermosetting resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Abstract
The invention provides a resin composition for a film for producing a film having excellent insulation and thermal conductivity. Provided is a resin composition for a film, which comprises a thermosetting resin (A) and hexagonal boron nitride secondary agglomerate particles (B). Wherein the hexagonal boron nitride secondary agglomerate (B) comprises a hexagonal boron nitride secondary agglomerate (B-1) having a cohesive failure strength of 7MPa or more and a hexagonal boron nitride secondary agglomerate (B-2) having a cohesive failure strength of 3MPa or more and less than 7 MPa.
Description
Technical Field
The present invention relates to a resin composition for a film, a film with a substrate, a metal/resin laminate, a cured resin, a semiconductor device, and a method for producing a film.
Background
In recent years, miniaturization and high power of electronic components, electric parts, and the like have been advanced. Their heat dissipation design is one of the major technical problems. In particular, high thermal conduction of an insulating layer having low thermal conductivity is a significant problem.
As a method for increasing the thermal conductivity of the insulating layer, it is known to add an insulating inorganic filler to a resin forming the insulating layer. As the inorganic filler, a metal oxide such as alumina, a metal nitride such as aluminum nitride, or the like is generally used. The primary particles of boron nitride generally have a scaly shape. Therefore, the primary particles of boron nitride have high thermal conductivity in the plane direction. Therefore, in order to efficiently exhibit high thermal conductivity in the plane direction, it is known to form secondary particles by agglomerating scaly primary particles. By using such secondary particles, higher thermal conductivity can be obtained than in the case of using scale-like primary particles (Japanese patent laid-open publication No. 2010-157563, Japanese re-publication No. 2013-145961, etc.).
A resin composition containing a resin material for forming an insulating layer and an insulating inorganic filler is used for forming the insulating layer. However, films produced using resin compositions are sometimes used because of the benefits of handling properties.
Disclosure of Invention
Technical problem to be solved by the invention
From the viewpoint of thermal conductivity, it is preferable to add secondary particles of boron nitride as an insulating filler to the resin composition for a film. However, it has been found that an insulating layer formed of a film produced using a resin composition may not exhibit desired thermal conductivity.
In order to solve the problems of the prior art, an object of the present invention is to provide a resin composition for a film for use in the production of a film having excellent insulation properties and thermal conductivity.
Technical scheme for solving technical problem
The present inventors have conducted intensive studies in order to achieve the above object. The results thereof show that: since the secondary particles of boron nitride are easily broken, when the secondary particles are uniformly dispersed in the resin composition for a film, the secondary particles are broken, and thus the thermal conductivity of the film produced using the resin composition may be lowered. On the other hand, it is found that: if the breaking strength of the secondary particles is too high, the film cannot be sufficiently compressed even if the film produced is cured by pressure, and therefore, a cured product having high thermal conductivity may not be obtained.
The present invention is an invention made based on the knowledge, and provides a resin composition for a film comprising a thermosetting resin (A) and hexagonal boron nitride secondary agglomerate (B) comprising hexagonal boron nitride secondary agglomerate (B-1) having cohesive failure strength of 7MPa or more and hexagonal boron nitride secondary agglomerate (B-2) having cohesive failure strength of 3MPa or more and less than 7MPa
In the resin composition for a film of the present embodiment, the ratio (mass ratio) ((B-1)/(B-2)) of the hexagonal boron nitride secondary agglomerate (B-1) and the hexagonal boron nitride secondary agglomerate (B-2) is preferably 10 to 0.05.
The resin composition for a film of the present embodiment may contain alumina particles (C).
In the resin composition for a film of the present embodiment, the ratio (mass ratio) ((C)/(B)) of the alumina particles (C) and the hexagonal boron nitride secondary agglomerate (B) is preferably 1 or less.
The film resin composition of the present embodiment preferably contains a curing agent (D).
The present invention also provides a film formed from the resin composition for a film of the present embodiment.
The present invention also provides a film with a substrate, which has a layer formed on at least one surface of a plastic substrate and composed of the film resin composition of the present embodiment.
The present invention also provides a metal/resin laminate having a layer formed on at least one surface of a metal plate or a metal foil and composed of the film resin composition of the present embodiment.
The present invention also provides a cured resin obtained by curing the resin composition for a film of the present embodiment.
The present invention also provides a semiconductor device using the resin composition for a film of the present embodiment.
In addition, the present invention provides a method for producing a film, comprising: the resin composition for a film of the present embodiment is applied to at least one surface of a plastic substrate, a metal plate, or a metal foil to form a film.
Effects of the invention
According to the resin composition for a film of the present embodiment, a film having excellent insulation properties and thermal conductivity can be formed. The film having excellent insulating properties and thermal conductivity is suitable for use as an interlayer adhesive for semiconductor devices and the like.
Detailed Description
The present embodiment will be described in detail below.
The resin composition for a film of the present embodiment includes a thermosetting resin (a) and hexagonal boron nitride secondary agglomerate particles (B). The components of the film resin composition of the present embodiment are described below.
(A) Thermosetting resin
(A) The thermosetting resin of the component (a) is not particularly limited. However, the curing temperature is preferably 80 ℃ to 250 ℃ and more preferably 130 ℃ to 200 ℃. When the curing temperature is higher than 250 ℃, there are disadvantages that deformation of the bonded parts occurs and the resin in the film flows out to fail to obtain sufficient adhesion. On the other hand, when the curing temperature is lower than 80 ℃, a curing reaction occurs in the step of coating and drying the film. Therefore, there is a problem that sufficient adhesiveness is not obtained when the member is adhered.
(A) The thermosetting resin of the component (a) is a compound having one or more functional groups contributing to curing in the molecule. The functional groups are reacted by heating to form a three-dimensional network structure. Thereby, curing is performed. From the viewpoint of the properties of the cured product, it is preferable that one molecule contains two or more functional groups. Examples of the thermosetting resin of the component (a) include phenol resins, urea resins, melamine resins, alkyd resins, unsaturated polyester resins, vinyl ester resins, epoxy resins, urethane resins, silicone resins, and polyimide resins. Among them, epoxy resins are preferable.
Examples of epoxy resins include: bisphenol compounds such as bisphenol a, bisphenol F, and bisphenol, and derivatives thereof (e.g., alkylene oxide adducts); diols having an alicyclic structure such as hydrogenated bisphenol a, hydrogenated bisphenol F, hydrogenated bisphenol, cyclohexanediol, cyclohexanedimethanol, and cyclohexanediol, and derivatives thereof; aliphatic diols such as butanediol, hexanediol, octanediol, nonanediol, and decanediol, and derivatives thereof; a polyfunctional epoxy resin having two or more glycidyl groups obtained by epoxidizing fluorene, a fluorene derivative, or the like; a polyfunctional epoxy resin having a trihydroxyphenylmethane skeleton or an aminophenol skeleton and having two or more glycidyl groups; and polyfunctional epoxy resins obtained by epoxidizing phenol novolac resins (phenol novolac resins), cresol novolac resins, phenol aralkyl resins (phenol aralkyl resins), biphenyl aralkyl resins, naphthol aralkyl resins, and the like. However, the epoxy resin used in the present embodiment is not limited to these examples. From the viewpoint of increasing the glass transition temperature (Tg), an epoxy resin having a fluorene skeleton is preferable. In addition, from the viewpoint of heat resistance, an epoxy resin having an aminophenol skeleton is preferable.
The epoxy resin may be a resin that is solid at room temperature or a resin that is liquid at room temperature. Both may be used in combination. However, from the viewpoint of film-forming properties of the film, an epoxy resin containing a resin that is liquid at room temperature is preferred.
(A) The thermosetting resin of component (b) preferably contains a polymer component such as a phenoxy resin. By containing the polymer component, advantages such as stable uncured film shape and easy handling of the film during film formation and before curing can be obtained.
When a phenoxy resin is used as the thermosetting resin of the component (a), various phenoxy resins such as a bisphenol a type phenoxy resin, a bisphenol F type phenoxy resin, and a bisphenol a-bisphenol F copolymerization type phenoxy resin can be used.
When a phenoxy resin is used as the thermosetting resin of the component (a), the weight average molecular weight (Mw) of the phenoxy resin is preferably 10000 to 200000.
When the thermosetting resin of component (a) is a combination of an epoxy resin and a phenoxy resin, the ratio of the epoxy resin to the phenoxy resin (mass of epoxy resin)/(mass of phenoxy resin) is preferably 0.01 to 50, more preferably 0.1 to 10, and still more preferably 0.2 to 5.
(B) Hexagonal boron nitride secondary agglomerate
The hexagonal boron nitride secondary agglomerate is added for the purpose of improving the thermal conductivity of a film produced using the film resin composition.
In the resin composition for a film of the present embodiment, the hexagonal boron nitride secondary agglomerate as the component (B) is used in combination with two kinds of particles having different cohesive failure strengths, specifically, the hexagonal boron nitride secondary agglomerate (B-1) having a cohesive failure strength of 7MPa or more and the hexagonal boron nitride secondary agglomerate (B-2) having a cohesive failure strength of 3MPa or more and less than 7 MPa.
As shown in examples described later, when only hexagonal boron nitride secondary agglomerate having a cohesive failure strength of 7MPa or more is used, the secondary agglomerate is difficult to be broken when the resin composition for a film is hot-pressed. Therefore, the film is not sufficiently compressed, and thus a predetermined thermal conductivity cannot be obtained.
On the other hand, when only hexagonal boron nitride secondary agglomerate particles having cohesive failure strength of less than 7MPa are used, a part of the secondary agglomerate particles may be broken during the preparation of the coating liquid such as mixing and dispersion. Therefore, a predetermined thermal conductivity cannot be obtained in this case, too.
In contrast, in the resin composition for a film of the present embodiment, the hexagonal boron nitride secondary agglomerate (B-1) having a cohesive failure strength of 7MPa or more and the hexagonal boron nitride secondary agglomerate (B-2) having a cohesive failure strength of 3MPa or more and less than 7MPa are used in combination. Thus, even if a part of the secondary agglomerate (B-2) having a cohesive failure strength of 3MPa or more and less than 7MPa collapses during the preparation of the coating liquid such as mixing and dispersion, the secondary agglomerate (B-1) having a cohesive failure strength of 7MPa or more is difficult to collapse, so that a sufficient amount of agglomerate exists in the resin composition for films. Further, at the time of hot pressing, since the secondary agglomerate (B-2) having a cohesive failure strength of 3MPa or more and less than 7MPa is present in the film, the film is easily compressed. Therefore, a predetermined thermal conductivity can be obtained.
Further, as shown in examples described later, in the case of using hexagonal boron nitride secondary agglomerate having a cohesive failure strength of 7MPa or more and hexagonal boron nitride secondary agglomerate having a cohesive failure strength of less than 3MPa in combination, the secondary agglomerate having a cohesive failure strength of less than 3MPa is caused to collapse during the preparation of a coating liquid such as mixing and dispersion. Therefore, a predetermined thermal conductivity cannot be obtained in this case, too.
In the resin composition for a film of the present embodiment, the preferred ratio (mass ratio) ((B-1)/(B-2)) of the hexagonal boron nitride secondary agglomerate (B-1) and the hexagonal boron nitride secondary agglomerate (B-2) is 10 to 0.05. When the ratio (mass ratio) of the two is more than 10 ((B-1)/(B-2)), the film cannot be sufficiently compressed when the resin composition for a film is hot-pressed. Therefore, there is a problem that a predetermined thermal conductivity cannot be obtained. When the ratio (mass ratio) of the two (B-1)/(B-2)) is less than 0.05, part of the secondary agglomerate particles (B-2) having a cohesive failure strength of 3MPa or more and less than 7MPa, which occupy the majority of the particles of component (B), is broken up during the preparation of the coating liquid such as mixing and dispersing. Therefore, there is a problem that a predetermined thermal conductivity cannot be obtained.
The ratio (mass ratio) of the both (B-1)/(B-2)) is more preferably 1 to 0.1, still more preferably 0.7 to 0.2.
In the resin composition for a film of the present embodiment, the hexagonal boron nitride secondary agglomerate of the component (B) is preferably contained in an amount of 40 to 80 mass% based on the mass% of the total mass of all the components of the resin composition for a film. When the content is less than 40 mass%, the amount of the thermally conductive filler in the film is insufficient, and there is a problem that a predetermined thermal conductivity cannot be obtained after hot pressing. When the content exceeds 80% by mass, it is difficult to maintain the shape of the film since the film produced using the resin composition for a film is easily damaged. Therefore, handling of the film becomes difficult. (B) The content of the hexagonal boron nitride secondary agglomerate of the component (b) is more preferably 45 to 70% by mass, and still more preferably 50 to 60% by mass.
(C) Alumina particles
The resin composition for a film of the present embodiment may further contain alumina particles (C). By adding alumina particles as the component (C), the film produced using the film resin composition has a large specific gravity. This can improve not only the thermal conductivity but also the film forming property. As a result, the breakdown voltage can be increased.
In the resin composition for a film of the present embodiment, when alumina particles are contained as the component (C), the ratio (mass ratio) of the hexagonal boron nitride secondary agglomerate of the component (C) and the component (B) ((C)/(B)) is preferably 1 or less. When the ratio (mass ratio) of the alumina particles of the component (C) to the component (B) ((C)/(B)) exceeds 1, there is a problem that a predetermined thermal conductivity cannot be obtained. The ratio (mass ratio) ((C)/(B)) is more preferably 0.6 or less, and still more preferably 0.1 to 0.4.
When the component (C) contains alumina particles, the particle diameter thereof is not particularly limited. However, it is preferable to use alumina particles having a particle diameter smaller than the film thickness of a film produced using the resin composition for a film. When the particle size of the alumina particles of component (C) is larger than the film thickness of the film produced using the film resin composition, there is a problem that the breakdown voltage of the film produced using the film resin composition is lowered.
(C) The alumina particles of component (b) more preferably have a particle diameter of 1/2 or less of the film thickness of a film produced using the film resin composition.
(C) The shape of the alumina particles of the component (a) is not particularly limited. Alumina particles having any shape such as spherical, round, plate-like, and fibrous shapes can be used.
The film resin composition of the present embodiment may further contain the following components as optional components.
(D) Curing agent
The resin composition for a film of the present embodiment may contain the component (D) as a curing agent for the thermosetting resin of the component (a). When the thermosetting resin of the component (a) is an epoxy resin, examples of the component (D) which is a curing agent that can be used include a phenol-based curing agent, an amine-based curing agent, an imidazole-based curing agent, and an acid anhydride-based curing agent. Among them, imidazole curing agents are preferable from the viewpoint of curability and adhesiveness to epoxy resins.
(other Components)
For the purpose of adjusting the dielectric constant, the linear expansion coefficient, the fluidity of the resin, the flame retardancy, and the like, the hexagonal boron nitride secondary agglomerate of the component (B) and the inorganic filler other than the alumina particle of the component (C) may be added to the resin composition for a film of the present embodiment, and for example, silicon oxide, magnesium oxide, zinc oxide, magnesium hydroxide, aluminum nitride, silicon nitride, diamond, silicon carbide, or the like may be added.
Further, a silane compound for the purpose of adjusting the adhesion, uniform dispersion of an inorganic additive, or the like may be added, or a dispersant or a rheology control agent for the purpose of preventing the coating liquid from settling may be added.
The resin composition for a film of the present embodiment is obtained by dissolving or dispersing a raw material containing the components (a) and (B), the components (C) and (D) added as needed, and other components in an organic solvent or the like. The method for dissolving or dispersing these raw materials is not particularly limited. However, it is preferable that the raw material is stirred at a low speed by a planetary stirrer or the like and then dispersed by a capillary wet dispersing device or the like. When the raw material is dispersed by using a bead mill, a ball mill or the like, the secondary agglomerate is broken down, and thus there is a problem that a predetermined thermal conductivity cannot be obtained.
The film of the present embodiment is formed using the resin composition for a film. Specifically, the film is formed by applying the resin composition for a film to at least one surface of a desired support and then drying the applied resin composition. The material of the support is not particularly limited. Examples of such materials include metal plates and metal foils such as copper and aluminum; and plastic substrates such as polyester resins, polyethylene resins, and polyethylene terephthalate resins. These supports may be subjected to a mold release treatment with a silicon compound or the like.
Further, the film with a substrate of the present embodiment can be obtained by forming a layer composed of the resin composition of the present embodiment on at least one surface of a plastic substrate.
On the other hand, the metal/resin laminate of the present embodiment can be obtained by forming a layer composed of the resin composition of the present embodiment on at least one surface of a metal plate or a metal foil.
The method for coating the resin composition for a film on the support is not particularly limited. However, from the viewpoint of film formation and film thickness control, it is preferable to use a micro gravure coating method, a slot die coating method, or a doctor blade method. A film having a thickness of, for example, 5 to 500 μm can be obtained by the slit die coating method.
The drying conditions may be appropriately set depending on the kind and amount of the organic solvent used in the resin composition for a film, the thickness of the coating, and the like. For example, the drying can be performed at 50 to 120 ℃ for 1 to 30 minutes. The film thus obtained had good storage stability. Further, the film may be peeled off from the support at a desired timing.
The film obtained by the above-mentioned step can be thermally cured for 30 to 180 minutes at a temperature of, for example, 80 ℃ to 250 ℃, preferably 130 ℃ to 200 ℃.
The thickness of the film obtained by the above-described step is preferably 5 μm or more and 500 μm or less. When the thickness of the film is less than 5 μm, there is a problem that film characteristics required for insulation and the like cannot be obtained. When the thickness exceeds 500. mu.m, the thermal conductivity of the film decreases. Therefore, when the film is used for interlayer bonding of a semiconductor device or the like, there is a problem that heat dissipation of the semiconductor device or the like becomes insufficient. The thickness of the film is more preferably 10 μm to 400 μm, and still more preferably 50 μm to 300 μm.
The film of the present embodiment has excellent thermal conductivity after curing. Specifically, the film of the present embodiment preferably has a thermal conductivity of 9W/m.K or more after curing. If the thermal conductivity is less than 9W/m.K, the heat dissipation of the semiconductor device or the like becomes insufficient when the film is used for interlayer bonding of the semiconductor device or the like. More preferably, the film of the present embodiment has a thermal conductivity of 11W/m · K or more after curing.
The film of the present embodiment has excellent insulating properties after curing. Specifically, the film of the present embodiment preferably has a breakdown voltage of 5kV/100 μm or more after curing. If the breakdown voltage is less than 5 kV/100. mu.m, there is a problem that the insulation properties required for a semiconductor device or the like cannot be satisfied. More preferably, the film of the present embodiment has a breakdown voltage of 7kV/100 μm or more after curing.
The film resin composition of the present embodiment is used for interlayer adhesion between constituent elements of a semiconductor device of the present embodiment. Specifically, the resin composition for a film of the present embodiment is used for, for example, interlayer adhesion between a substrate and a heat sink, interlayer adhesion between an electronic component and a substrate, or an insulating layer covering the electronic component. Alternatively, a film formed from the film resin composition of the present embodiment, a film with a substrate on which a layer formed from the film resin composition is formed, or a metal/resin laminate on which a layer formed from the film resin composition is formed is used in a device including an electronic component.
Examples
Hereinafter, this embodiment will be described in detail with reference to examples. However, the present embodiment is not limited to this.
(examples 1 to 9 and comparative examples 1 to 3)
The thermosetting resin of component (a), other additives and methyl ethyl ketone as an organic solvent were charged into a planetary mixer at the compounding ratios shown in table 1, and stirred for 30 minutes. Then, the hexagonal boron nitride secondary agglomerate of the component (B) and the alumina particle of the component (C) were put in and stirred for 1 hour. Further, the curing agent of component (D) was added thereto and stirred for 10 minutes. The obtained mixed solution was dispersed by a wet-type micronizer (MN2-2000AR Giltamida Seisakusho Co., Ltd.) to obtain a coating liquid containing a resin composition. A film having a thickness of about 100 μm was produced by applying the obtained coating liquid containing the resin composition to one surface of a plastic substrate (PET film subjected to mold release treatment).
The components used in the preparation of the resin composition for a film are as follows.
(A) The components: thermosetting resin
(A-1): liquid epoxy resin, product name 630, manufactured by Mitsubishi chemical corporation
(A-2): solid epoxy resin, brand name CG-500, manufactured by Osaka gas chemical Co., Ltd
(A-3): phenoxy resin, product name YX7200, manufactured by Mitsubishi chemical corporation
(B) The components: hexagonal boron nitride secondary agglomerate
(B-1 a): product name FP-40 (ultra high strength product) manufactured by electrochemical Co., Ltd., cohesive failure strength 8.2MPa
(B-1B): product name FP-70 (ultra high strength product) manufactured by electrochemical Co., Ltd., cohesive failure strength 7.7MPa
(B-2): HP-40MF100, a product of Shuizhiki alloy Co., Ltd., cohesive failure strength of 4.8MPa
(B'): product name FP-40 (general Strength product), manufactured by electrochemical Co., Ltd., cohesive fracture strength 1.3MPa
Further, the cohesive failure strength of the hexagonal boron nitride secondary agglomerate of the (B) component was measured by the method shown below.
A micro compression tester (product name MCT-510, manufactured by Shimadzu corporation) was used for the measurement. In the course of increasing the compressive force at a load speed of 0.8924mN/s, the point at which the displacement changes greatly was judged as a test force for agglomerate destruction. From the test force and the size of the particles, the cohesive failure strength of the particles was calculated by the following formula.
Cs(Pa)＝2.48×P/πd2
Cs: cohesive Strength of failure (Pa)
P: test force at failure Point (N)
d: measured diameter (mm) of the measured particle
Further, the cohesive failure strength of each species was determined by measuring the cohesive failure strengths of 10 samples randomly taken out from the hexagonal boron nitride secondary agglomerate of the same species. The average of these 10 measurements was taken as the cohesive failure strength for this species.
(C) The components: alumina particles
(C-1): the product was named DAW0735, manufactured by Kogyo Kabushiki Kaisha (average particle size: 7 μm)
(D) The components: curing agent
(D-1) product name EH-2021, imidazole curing agent, manufactured by Siguo Kasei Kogyo K.K.)
(D-2) name 2PHZPW, imidazole-based curing agent, manufactured by Siguo Kasei Kogyo
(E) The components: other ingredients
(E-1) dispersant ED216, Nanben Kabushiki Kaisha
(E-2) silane coupling agent, product name KBM403, manufactured by shin-Etsu chemical Co., Ltd
(E-3): rheology control agent, product name BYK-410, manufactured by Nikko chemical Co., Ltd
The coating liquid and the film with a substrate prepared and produced by the above steps were evaluated by the following methods.
< evaluation of film Forming Property >
Using the coating liquid prepared by the procedure, a film was formed with a blade coater at a line speed of 0.5 m/min. The state of the uncured film obtained by drying at 90 ℃ for 10 minutes was observed. The results were evaluated according to the following criteria.
B: can be beautifully formed into a film
C: can form a film, but is slightly brittle and requires attention during handling
D: can not form a film
< method for measuring thermal conductivity >
The film is laminated so that the film has a thickness of 300 to 600 μm. The cured film is produced by vacuum pressing at 180 ℃ for 1 hour (pressure at the time of press curing is 5 to 10 MPa). The specific gravity of the film was measured by the archimedes method. The cured film was cut into 10mm squares, and then the thermal diffusion coefficient was measured using a thermal conductivity measuring apparatus (manufactured by shin-Nippon Co., Ltd.). Further, the thermal conductivity was calculated by the following formula using the specific heat determined by another method.
Thermal conductivity (W/m.k) thermal diffusion coefficient x specific heat x specific gravity
The obtained results were evaluated according to the following criteria.
A: 11 (W/m.K) or more
B: 9 (W/m.K) or more and less than 11 (W/m.K)
D: less than 9 (W/m. K)
< method for measuring breakdown Voltage >
The cured film is produced by vacuum pressing (pressure at the time of press curing is 5 to 10MPa) at 180 ℃ for 1 hour. The breakdown voltage was measured using a device (product name: DAC-WT-50, manufactured by TOYOBO Co., Ltd.). The voltage at which the insulating layer broke was measured while applying a voltage of 200V/s between the electrodes sandwiching the cured film. In addition, the measurement was performed 5 times. The average of the obtained measurements was determined as the breakdown voltage of the composition.
The obtained results were evaluated according to the following criteria.
A: 7(kV/100 μm) or more
B: 5(kV/100 μm) or more and less than 7(kV/100 μm)
D: less than 5(kV/100 μm)
The results are shown in the following table.
[ Table 1]
[ Table 2]
Examples 1 to 9 all showed film forming properties of C or more. In addition, these examples all show thermal conductivity above B and breakdown voltage. Further, in examples 2, 3 and 5, the compounding ratio of the hexagonal boron nitride secondary agglomerate (B-1) and (B-2) was different from that of example 1. In example 4, the kind of hexagonal boron nitride secondary agglomerate (B-1) having a cohesive failure strength of 7MPa or more is different from that of the other examples. In examples 6 to 9, alumina particles (C) were added, unlike in the other examples. In comparative example 1 in which only the hexagonal boron nitride secondary agglomerate (B-1) was added, comparative example 2 in which only the hexagonal boron nitride secondary agglomerate (B-2) was added, and comparative example 3 in which hexagonal boron nitride secondary agglomerate (B') having a cohesive failure strength of less than 3MPa was added in place of the hexagonal boron nitride secondary agglomerate (B-2), the thermal conductivity was D.
The resin composition for films according to the embodiment of the present invention may be the following first to fifth resin compositions for films.
The resin composition for a first film comprises a thermosetting resin (A) and hexagonal boron nitride secondary agglomerate (B) comprising hexagonal boron nitride secondary agglomerate (B-1) having a cohesive failure strength of 7MPa or more and hexagonal boron nitride secondary agglomerate (B-2) having a cohesive failure strength of 3MPa or more and less than 7 MPa.
The second film resin composition is the first film resin composition, wherein the ratio (mass ratio) ((B-1)/(B-2)) of the hexagonal boron nitride secondary agglomerate (B-1) to the hexagonal boron nitride secondary agglomerate (B-2) is 10 to 0.05.
The third film resin composition is the first film resin composition or the second film resin composition, wherein the film resin composition further contains alumina particles (C).
The fourth film resin composition is the third film resin composition, wherein the ratio (mass ratio) ((C)/(B)) of the alumina particles (C) and the hexagonal boron nitride secondary agglomerate particles (B) is 1 or less.
The fifth film resin composition is any one of the first to fourth film resin compositions, and further includes a curing agent (D).
The film according to the embodiment of the present invention may be a film formed from any one of the first to fifth film resin compositions.
The film with a substrate according to the embodiment of the present invention may be a film with a substrate in which a layer made of any one of the first to fifth film resin compositions is formed on at least one surface of a plastic substrate.
The metal/resin laminate according to the embodiment of the present invention may be a metal/resin laminate in which a layer made of any one of the first to fifth film resin compositions is formed on at least one surface of a metal plate or a metal foil.
The cured resin material according to the embodiment of the present invention may be a cured resin material obtained by curing any one of the first to fifth film resin compositions.
The semiconductor device according to the embodiment of the present invention may be a semiconductor device using any one of the resin compositions for a first film to the resin composition for a fifth film.
The film production method according to the embodiment of the present invention may be a film production method including: the film is formed by applying any one of the first to fifth film resin compositions to at least one surface of a plastic substrate, a metal plate, or a metal foil.
Claims (11)
1. A resin composition for a film, characterized in that,
the resin composition for a film comprises a thermosetting resin (A) and hexagonal boron nitride secondary agglomerate particles (B),
the hexagonal boron nitride secondary agglomerate (B) comprises a hexagonal boron nitride secondary agglomerate (B-1) having a cohesive failure strength of 7MPa or more and a hexagonal boron nitride secondary agglomerate (B-2) having a cohesive failure strength of 3MPa or more and less than 7 MPa;
wherein the mass ratio (B-1)/(B-2) of the hexagonal boron nitride secondary agglomerate (B-1) to the hexagonal boron nitride secondary agglomerate (B-2) is 0.1 to 0.7,
and further comprising 45 to 70 mass% of hexagonal boron nitride secondary agglomerate of component (B) based on the total mass% of all the components of the resin composition for film,
and wherein the cohesive failure strength is measured as follows: using a micro compression tester, a point at which the displacement changes greatly in the process of increasing the compression force at a load speed of 0.8924N/s was determined as a test force for aggregate fracture, and the cohesive fracture strength of the particles was calculated from the test force and the size of the particles by the following equation:
Cs＝2.48×P/πd2wherein, in the step (A),
cs: cohesive failure strength in Pa;
p: the test force at the point of failure in units of N;
d: the measured diameter of the measured particles is in mm.
2. The resin composition for a film according to claim 1, wherein the resin composition for a film comprises alumina particles (C).
3. The resin composition for a film according to claim 2,
the mass ratio (C)/(B) of the alumina particles (C) to the hexagonal boron nitride secondary agglomerate particles (B) is 1 or less.
4. The resin composition for a film according to claim 1 or 2,
the resin composition for a film contains a curing agent (D).
5. The resin composition for a film according to claim 3,
the resin composition for a film contains a curing agent (D).
6. A film characterized by a film comprising, in combination,
the film is formed from the resin composition for film according to any one of claims 1 to 5.
7. A film with a substrate, characterized in that,
the film with a substrate has a layer formed on at least one surface of a plastic substrate and composed of the resin composition for a film according to any one of claims 1 to 5.
8. A metal/resin laminate characterized in that,
the metal/resin laminate comprises a layer formed on at least one surface of a metal plate or a metal foil and composed of the film resin composition according to any one of claims 1 to 5.
9. A cured resin material characterized by comprising,
the cured resin is obtained by curing the resin composition for a film according to any one of claims 1 to 5.
10. A semiconductor device is characterized in that a semiconductor element,
the semiconductor device uses the resin composition for a film according to any one of claims 1 to 5.
11. A method of manufacturing a film, comprising:
a film formed by applying the resin composition for a film according to any one of claims 1 to 5 to at least one surface of a plastic substrate, a metal plate or a metal foil.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-133027 | 2016-07-05 | ||
| JP2016133027 | 2016-07-05 | ||
| PCT/JP2017/023454 WO2018008450A1 (en) | 2016-07-05 | 2017-06-26 | Resin composition for films, film, film with base, metal/resin laminate, resin cured product, semiconductor device, and method for producing film |
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| Publication Number | Publication Date |
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| CN109312164A CN109312164A (en) | 2019-02-05 |
| CN109312164B true CN109312164B (en) | 2022-05-03 |
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| Country | Link |
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| US (1) | US20190160785A1 (en) |
| JP (1) | JP6945241B2 (en) |
| KR (1) | KR102305674B1 (en) |
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| JP7103938B2 (en) * | 2017-01-30 | 2022-07-20 | 積水化学工業株式会社 | Resin material and laminate |
| JP6974301B2 (en) * | 2017-01-30 | 2021-12-01 | 積水化学工業株式会社 | Resin material and laminate |
| WO2018139642A1 (en) * | 2017-01-30 | 2018-08-02 | 積水化学工業株式会社 | Resin material and laminate |
| WO2019168155A1 (en) * | 2018-03-01 | 2019-09-06 | 積水化学工業株式会社 | Laminated body |
| WO2020004225A1 (en) * | 2018-06-26 | 2020-01-02 | 京セラ株式会社 | Organic substrate, metal-clad laminate and wiring board |
| JP7431574B2 (en) | 2018-12-21 | 2024-02-15 | 積水化学工業株式会社 | laminate |
| JP7304167B2 (en) * | 2019-02-13 | 2023-07-06 | デンカ株式会社 | Method for manufacturing insulating sheet, method for manufacturing metal-based circuit board, and insulating sheet |
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- 2017-06-26 US US16/312,054 patent/US20190160785A1/en not_active Abandoned
- 2017-06-26 KR KR1020187036669A patent/KR102305674B1/en active IP Right Grant
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| Publication number | Publication date |
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| KR102305674B1 (en) | 2021-09-27 |
| TWI794179B (en) | 2023-03-01 |
| JPWO2018008450A1 (en) | 2019-05-30 |
| TW201821503A (en) | 2018-06-16 |
| US20190160785A1 (en) | 2019-05-30 |
| KR20190026672A (en) | 2019-03-13 |
| JP6945241B2 (en) | 2021-10-06 |
| CN109312164A (en) | 2019-02-05 |
| WO2018008450A1 (en) | 2018-01-11 |
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